KR102655911B1 - Heterocyclic compound, organic electronic device comprising the same and method for manufacturing organic electronic device using the same - Google Patents

Abstract

This specification relates to a heterocyclic compound represented by Formula 1, an organic electronic device including the heterocyclic compound in an organic active layer, and a method of manufacturing an organic electronic device using the heterocyclic compound.

Description

Heterocyclic compound, organic electronic device containing same, and method of manufacturing organic electronic device using same {HETEROCYCLIC COMPOUND, ORGANIC ELECTRONIC DEVICE COMPRISING THE SAME AND METHOD FOR MANUFACTURING ORGANIC ELECTRONIC DEVICE USING THE SAME}

This specification relates to heterocyclic compounds, organic electronic devices containing the same, and methods for manufacturing organic electronic devices using the same.

In this specification, an organic electronic device is an electronic device using an organic semiconductor material and requires exchange of holes and/or electrons between an electrode and an organic semiconductor material. Organic electronic devices can be broadly divided into two categories according to their operating principles as follows. First, excitons are formed in the organic layer by photons flowing into the device from an external light source, these excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes and used as current sources (voltage sources). It is a type of electronic device. The second is an electronic device that applies voltage or current to two or more electrodes to inject holes and/or electrons into the organic semiconductor material layer forming the interface with the electrodes, and operates by the injected electrons and holes.

Examples of organic electronic devices include organic solar cells, organic photovoltaic devices, organic light-emitting devices, organic photoreceptors (OPCs), and organic transistors, which all use electron/hole injection materials, electron/hole extraction materials, and electrons to drive the devices. /Requires hole transport material or light emitting material. Hereinafter, organic solar cells will be mainly described in detail, but in the organic electronic devices, electron/hole injection materials, electron/hole extraction materials, electron/hole transport materials, or light-emitting materials all operate on similar principles.

Solar cells are batteries that change electrical energy directly from sunlight, and research is actively underway because they are a clean alternative energy source to solve global environmental problems caused by the depletion of fossil energy and its use. Here, a solar cell refers to a battery that absorbs light energy from sunlight and generates current-voltage using the photovoltaic effect, which generates electrons and holes.

A solar cell is a device that can directly convert solar energy into electrical energy by applying the photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the materials that make up the thin film.

Much research is being conducted to increase energy conversion efficiency through changes in various layers and electrodes according to the design of solar cells.

Two-layer organic photovoltaic cell (C.W.Tang, Appl. Phys. Lett., 48, 183. (1986)) Efficiencies via Network of Internal Donor-Acceptor Heterojunctions (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995))

The purpose of the present invention is to provide a heterocyclic compound, an organic electronic device containing the same, and a method for manufacturing an organic electronic device using the same.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1 to R14 are each hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

Any one of R9 to R11; And any one of R12 to R14 is each a substituted or unsubstituted alkoxy group,

Any other of R9 to R11; and any other of R12 to R14 is each a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylthio group,

L1 to L4 are each a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

Ar1 and Ar2 are each a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,

Y1 and Y2 are each hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n and m are each integers from 0 to 6.

In addition, one embodiment of the present specification is

first electrode;

a second electrode provided opposite the first electrode; and

It is provided between the first electrode and the second electrode, and includes one or more organic layers including an organic active layer,

The organic active layer provides an organic electronic device including the heterocyclic compound.

In addition, one embodiment of the present specification is

forming a first electrode on a substrate;

forming one or more organic layers including an organic active layer on the first electrode; and

Comprising the step of forming a second electrode on the organic layer,

The organic active layer provides a method of manufacturing an organic electronic device, wherein the organic active layer includes the heterocyclic compound.

In an exemplary embodiment of the present specification, the heterocyclic compound has a wide light absorption area and a high LUMO energy level, so when the heterocyclic compound is used in the organic active layer of an organic electronic device, a high level of photo-electric conversion efficiency can be obtained. You can.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification.
Figures 2 to 61 each show UV-Vis spectra of the film state of compounds 1 to 60 prepared in the preparation examples of the present specification.

Hereinafter, this specification will be described in more detail.

An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1 to R14 are each hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Or a substituted or unsubstituted alkylthio group,

Any one of R9 to R11; And any one of R12 to R14 is each a substituted or unsubstituted alkoxy group,

Any other of R9 to R11; and any other of R12 to R14 is each a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkylthio group,

L1 to L4 are each a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

Ar1 and Ar2 are each a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,

Y1 and Y2 are each hydrogen; halogen group; Or a substituted or unsubstituted alkyl group,

n and m are each integers from 0 to 6.

Conventional research on organic electronic devices has focused on finding electron donor materials that produce high efficiency when the electron acceptor of the organic active layer is a fullerene compound such as PCBM. However, organic electronic devices containing fullerene compounds have low absorption area, open-circuit voltage, and Because limitations are being encountered in performance such as device lifespan, research on using non-fullerene compounds such as ITIC as electron acceptors is increasing.

Most non-fullerene compounds are composed of EWG (electron withdrawing group)-EDG (electron donating group)-EWG (electron withdrawing group), and the thiophene of the two-dimensional structure of EDG is composed of an alkylthio group or a thiophene substituted with an alkyl group. When a group is included, the absorption area is expanded, including increased solubility, and there is an advantage in that the energy level can be adjusted. However, there is a limit to energy level control with the alkylthio group or alkyl group. To solve this problem, the inventors of the present invention confirmed that optical and electrochemical improvements were achieved and solubility was improved by introducing an alkoxy group into thiophene as shown in Chemical Formula 1 above. It was discovered that because it has these various advantages, it can ultimately increase the efficiency and stability of organic electronic devices, including organic solar cells.

In this specification, when a part 'includes' a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

In this specification, when a member is said to be located 'on' another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In this specification, energy level refers to the amount of energy. Therefore, even when the energy level is displayed in the minus (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, the HOMO energy level means the distance from the vacuum level to the highest occupied molecular orbital. Additionally, the LUMO energy level refers to the distance from the vacuum level to the lowest unoccupied molecular orbital.

In this specification, the term 'substitution' means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, 2 In the case of more than one substitution, two or more substituents may be the same or different from each other.

In this specification, the term 'substituted or unsubstituted' refers to deuterium; halogen group; hydroxyl group; Alkyl group; Cycloalkyl group; Alkoxy group; Aryloxy group; alkenyl group; Aryl group; and a heterocyclic group, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituent.

In the present specification, the number of carbon atoms of a substituent having a branched chain includes the number of carbon atoms of the branched chain. For example, in 'an alkyl group having 3 to 20 carbon atoms having one or more methyl groups as a branch', '3 to 20' is a number including the number of carbon atoms of the 'one or more methyl groups'.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl , 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, Examples include, but are not limited to, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylhexyl, 4-methylhexyl, and 5-methylhexyl.

In the present specification, the alkylthio group may be straight chain, branched chain, or cyclic chain. The number of carbon atoms of the alkylthio group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methylthio, ethylthio, n-propylthio, isopropylthio, i-propylthio, n-butylthio, isobutylthio, tert-butylthio, sec-butylthio, n-pentylthio, neopentylthio. , isopentylthio, n-hexylthio, 3,3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio, and p-methylbenzylthio. , but is not limited to this.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, (3,3-dimethylbutyl)oxy, (2-ethylbutyl)oxy, (2-hexyldecyl)oxy, n-octyloxy, n-nonyloxy and n-decyloxy. Poems, etc., but are not limited to these.

In the present specification, the aryl group may be monocyclic or polycyclic.

In this specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, monocyclic aryl groups include phenyl groups, biphenyl groups, and terphenyl groups, but are not limited thereto.

In this specification, when the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable to have 10 to 30 carbon atoms. Specifically, polycyclic aryl groups include, but are not limited to, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, and fluorenyl group. The fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and a heteroatom. Specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group , benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzo. furanyl groups, etc., but are not limited to these.

The heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic.

In the present specification, the description regarding the heterocyclic group described above may be applied, except that the heteroaryl group is aromatic.

In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group.

The aromatic hydrocarbon ring and heterocycle located at Ar1 and Ar2 are excluded from being monovalent groups, and may be, for example, a divalent or higher aryl group or a divalent or higher heterocyclic ring.

In an exemplary embodiment of the present specification, L1 to L4 are each a phenylene group.

In an exemplary embodiment of the present specification, L1 to L4 each represent a divalent thiophene group.

In an exemplary embodiment of the present specification, L1 to L4 each represent a divalent selenophene group.

In one embodiment of the present specification, Formula 1 is represented by the following Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2,

R1 to R14, Ar1, Ar2, Y1, Y2, n and m are the same as defined in Formula 1 above,

Q1 to Q4 are S or Se, respectively.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are monocyclic or polycyclic aromatic hydrocarbon rings.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are substituted or unsubstituted benzene rings.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are substituted or unsubstituted naphthalene rings.

In one embodiment of the present specification, Ar1 and Ar2 are substituted or unsubstituted thiophene.

In one embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,

R1 to R14, L1 to L4, Y1, Y2, n and m are the same as defined in Formula 1 above,

R15 to R22 are each hydrogen; Or it is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 4-1 to 4-8.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

In Formulas 4-1 to 4-8,

R1 to R14, Y1, Y2, n and m are the same as defined in Formula 1 above,

R15 to R22 are each hydrogen; Or a substituted or unsubstituted alkyl group,

Q1 to Q4 are S or Se, respectively.

In an exemplary embodiment of the present specification, Q1 to Q4 are each S.

In an exemplary embodiment of the present specification, Y1 and Y2 are each hydrogen.

In one embodiment of the present specification, Y1 and Y2 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, Y1 and Y2 are each a methyl group.

In an exemplary embodiment of the present specification, Y1 and Y2 are each fluorine, chlorine, or bromine.

In an exemplary embodiment of the present specification, n and m are each integers from 0 to 2.

In an exemplary embodiment of the present specification, n and m are each 1.

In an exemplary embodiment of the present specification, n and m are each 2.

In an exemplary embodiment of the present specification, R1 to R4 are each a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain or branched alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R1 to R4 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R5 to R8 are each hydrogen.

In one embodiment of the present specification, R9 and R12 are each a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkylthio group, R10 and R13 are each a substituted or unsubstituted alkoxy group, and R11 and R14 are each hydrogen.

In one embodiment of the present specification, R9 and R12 are each an alkyl group having 1 to 20 carbon atoms; Or it is an alkylthio group having 1 to 20 carbon atoms.

In one embodiment of the present specification, R9 and R12 are each an alkyl group having 5 to 10 carbon atoms; Or it is an alkylthio group having 5 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R9 and R12 are each 2-ethylhexyl; or (2-ethylhexyl)thio.

In one embodiment of the present specification, R9 and R12 are each an alkylthio group having 1 to 20 carbon atoms, and in the case of an alkylthio group, there is an advantage of increasing device efficiency compared to an alkyl group.

In an exemplary embodiment of the present specification, R15 to R22 are each hydrogen.

In one embodiment of the present specification, R15 and R17 are each a straight-chain alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R15 and R17 are each a methyl group.

In an exemplary embodiment of the present specification, Formula 1 is any one selected from Formulas 5-1 to 5-60 below.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

[Formula 5-12]

[Formula 5-13]

[Formula 5-14]

[Formula 5-15]

[Formula 5-16]

[Formula 5-17]

[Formula 5-18]

[Formula 5-19]

[Formula 5-20]

[Formula 5-21]

[Formula 5-22]

[Formula 5-23]

[Formula 5-24]

[Formula 5-25]

[Formula 5-26]

[Formula 5-27]

[Formula 5-28]

[Formula 5-29]

[Formula 5-30]

[Formula 5-31]

[Formula 5-32]

[Formula 5-33]

[Formula 5-34]

[Formula 5-35]

[Formula 5-36]

[Formula 5-37]

[Formula 5-38]

[Formula 5-39]

[Formula 5-40]

[Formula 5-41]

[Formula 5-42]

[Formula 5-43]

[Formula 5-44]

[Formula 5-45]

[Formula 5-46]

[Formula 5-47]

[Formula 5-48]

[Formula 5-49]

[Formula 5-50]

[Formula 5-51]

[Formula 5-52]

[Formula 5-53]

[Formula 5-54]

[Formula 5-55]

[Formula 5-56]

[Formula 5-57]

[Formula 5-58]

[Formula 5-59]

[Formula 5-60]

In one embodiment of the present specification, the heterocyclic compound exhibits an absorption region of 300 nm to 1,000 nm, and preferably has a maximum absorption wavelength of 700 nm to 900 nm.

Accordingly, when applied to an organic electronic device, it exhibits complementary absorption to the absorption region (300 nm to 700 nm) of the electron donor, and thus can exhibit a high short-circuit current when applied to an organic electronic device.

In one embodiment of the present specification, the heterocyclic compound is capable of absorbing light in the visible light full-wave range and can also absorb light in the infrared range. Accordingly, the effect of having a wide absorption wavelength range of the device can be achieved.

An exemplary embodiment of the present specification includes a first electrode; a second electrode provided opposite the first electrode; and one or more organic material layers provided between the first electrode and the second electrode and including an organic active layer, wherein the organic active layer includes the heterocyclic compound.

Additionally, an exemplary embodiment of the present specification includes forming a first electrode on a substrate; forming one or more organic layers including an organic active layer on the first electrode; and forming a second electrode on the organic material layer, wherein the organic active layer includes the heterocyclic compound.

In one embodiment of the present specification, the method of manufacturing the organic electronic device may further include forming an electron transport layer on the first electrode.

In one embodiment of the present specification, the step of forming the organic layer is performed by spin-coating, slot die, blade coating, or roll-to-roll coating, preferably at a speed of 700 rpm to 1,300 rpm. It is carried out by coating method.

When the spin-coating speed is within the above range, the thickness of the organic active layer can be formed to be about 100 nm, thereby improving the performance of the organic electronic device.

The organic electronic device of the present invention can be manufactured by conventional organic electronic device manufacturing methods and materials, except that the heterocyclic compound represented by Formula 1 is included in the organic active layer.

In one embodiment of the present specification, the organic active layer includes an electron donor and an electron acceptor, and the electron acceptor includes the heterocyclic compound.

In this specification, the organic active layer may be a photoactive layer or a light-emitting layer.

In the present specification, the organic electronic device may be an organic solar cell, an organic photoelectric device, an organic light-emitting device, an organic photoreceptor (OPC), or an organic transistor.

Below, organic solar cells will be exemplified. In the organic solar cell, the organic active layer is a photoactive layer, and the above-mentioned organic electronic device can be referred to the description of the organic solar cell described later.

An exemplary embodiment of the present specification includes a first electrode; a second electrode provided opposite the first electrode; and one or more organic material layers provided between the first electrode and the second electrode and including a photoactive layer, wherein the photoactive layer includes the heterocyclic compound.

The organic solar cell may further include a substrate, a hole transport layer, a hole injection layer, an electron injection layer, and/or an electron transport layer.

In one embodiment of the present specification, the organic solar cell may further include an additional organic material layer. The organic solar cell can reduce the number of organic material layers by using organic materials that have multiple functions simultaneously.

In one embodiment of the present specification, the photoactive layer includes an electron donor and an electron acceptor, and the electron acceptor includes the heterocyclic compound.

In one embodiment of the present specification, the electron donor may use a material applied in the art, for example, poly 3-hexyl thiophene (P3HT), poly[N-9 (PCDTBT) '-heptadecanyl-2,7-carbazole-alt-5,5-(4'-7'-di-2-thienyl-2',1',3'-benzothiadiazole)]), PCPDTBT(poly[2,6 -(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] ), PFO-DBT(poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4,7-bis(thiophene-2-yl)benzo-2,1,3-thiadiazole)] ), PTB7 (Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2- [(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]), PSiF-DBT(Poly[2,7-(9,9-dioctyl-dibenzosilole)-alt-4,7-bis(thiophen -2-yl)benzo-2,1,3-thiadiazole]), PTB7-Th(Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl) ]) and PBDB-T (poly(benzodithiophene-benzotriazole)).

In one embodiment of the present specification, the electron donor is PBDB-T. The mass ratio of the electron donor and the electron acceptor may be 1:2 to 2:1, preferably 1:1.5 to 1.5:1, and more preferably 1:1.

In one embodiment of the present specification, the electron donor and electron acceptor may form a bulk heterojunction (BHJ). Bulk heterojunction means that electron donor materials and electron acceptor materials are mixed together in the photoactive layer.

In one embodiment of the present specification, the electron donor is a p-type organic material layer, and the electron acceptor is an n-type organic material layer.

In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode. In another embodiment, the first electrode is a cathode, and the second electrode is an anode.

In another embodiment, the organic solar cell may be arranged in the following order: an anode, hole transport layer, photoactive layer, electron transport layer, and cathode, or may be arranged in the order of cathode, electron transport layer, photoactive layer, hole transport layer, and anode. , but is not limited to this.

In one embodiment of the present specification, the organic solar cell has a normal structure. In the normal structure, a substrate, a first electrode, a hole transport layer, an organic material layer including a photoactive layer, an electron transport layer, and a second electrode may be stacked in that order.

In one embodiment of the present specification, the organic solar cell has an inverted structure. In the inverted structure, a substrate, a first electrode, an electron transport layer, an organic material layer including a photoactive layer, a hole transport layer, and a second electrode may be stacked in that order.

1 is a diagram showing an organic solar cell according to an exemplary embodiment of the present specification. According to FIG. 1, when light is incident from the first electrode 100 and/or the second electrode 300 and the photoactive layer 200 absorbs light in the entire wavelength range, an exciton is generated inside the organic solar cell. You can. Exciton is separated into holes and electrons in the photoactive layer 200, the separated holes move to the anode side, which is one of the first electrode 100 and the second electrode 300, and the separated electrons move to the first electrode 100 and the anode. It moves to the cathode side, which is the other one of the second electrodes 300, so that current can flow through the organic solar cell.

In one embodiment of the present specification, the organic solar cell has a tandem structure. In this case, the organic solar cell may include two or more photoactive layers.

The organic solar cell according to an exemplary embodiment of the present specification may have one or two or more layers of photoactive layers.

In another embodiment, a buffer layer may be provided between the photoactive layer and the hole transport layer or between the photoactive layer and the electron transport layer. At this time, a hole injection layer may be further provided between the anode and the hole transport layer. Additionally, an electron injection layer may be further provided between the cathode and the electron transport layer.

In one embodiment of the present specification, the substrate may be a glass substrate or a transparent plastic substrate with excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is limited to any substrate commonly used in organic solar cells. It doesn't work. Specifically, there are glass, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene), PI (polyimide), and TAC (triacetyl cellulose). It is not limited to this.

The material of the first electrode may be a transparent and highly conductive material, but is not limited thereto. For example, metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited to these. .

The method of forming the first electrode is not particularly limited, but for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade, or gravure printing can be used.

When forming the first electrode on a substrate, it may undergo cleaning, moisture removal, and hydrophilic modification processes.

For example, the patterned ITO substrate was sequentially cleaned with a detergent, acetone, and isopropyl alcohol (IPA), and then washed on a heating plate at 100°C to 150°C for 1 minute to 30 minutes, preferably at 120°C for 10 minutes to remove moisture. After drying and completely cleaning the substrate, the surface of the substrate is modified to be hydrophilic.

Through the above surface modification, the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Additionally, during modification, the formation of a polymer thin film on the first electrode may become easier and the quality of the thin film may be improved.

Pretreatment technologies for the first electrode include a) a surface oxidation method using parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet rays in a vacuum, and c) oxygen generated by plasma. There is a method of oxidation using radicals.

One of the above methods can be selected depending on the state of the first electrode or substrate. However, whichever method is used, it is generally desirable to prevent oxygen escape from the surface of the first electrode or substrate and to suppress the remaining moisture and organic matter as much as possible. At this time, the practical effect of pre-processing can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV light can be used. At this time, after ultrasonic cleaning, the patterned ITO substrate is baked on a hot plate and dried well, then placed in a chamber, and a UV lamp is applied to produce ozone generated when oxygen gas reacts with UV light. The patterned ITO substrate can be cleaned.

However, the method for modifying the surface of the patterned ITO substrate in this specification does not need to be particularly limited, and any method may be used as long as it oxidizes the substrate.

The second electrode may be a metal with a low work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; Alternatively, it may be a material with a multilayer structure such as LiF/Al, LiO ₂ /Al, LiF/Fe, Al:Li, Al:BaF ₂ , Al:BaF ₂ :Ba, but is not limited thereto.

The second electrode may be formed by depositing inside a thermal evaporator with a vacuum of 5 × 10 ^-7 torr or less, but the method is not limited to this method.

The hole transport layer and/or electron transport layer material serves to efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material is PEDOT:PSS (Poly(3,4-ethylenediocythiophene) doped with poly(styrenesulfonic acid)); Molybdenum oxide (MoO _x ); vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); and tungsten oxide (WO _x ), but is not limited to these.

The electron transport layer material may be BCP (bathocuproine) or electron-extracting metal oxides, and specifically, BCP (bathocuproine), a metal complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; Metal complexes containing Liq; LIF; Ca; Titanium oxide (TiO _x ); zinc oxide (ZnO); and cesium carbonate (Cs ₂ CO ₃ ), but is not limited to these.

In one embodiment of the present specification, a vacuum deposition method or a solution application method may be used as a method of forming the photoactive layer, and the solution application method refers to adding a photoactive material such as an electron donor and/or an electron acceptor in an organic solvent. This refers to a method of dissolving and then applying the solution using methods such as spin coating, dip coating, screen printing, spray coating, doctor blade, and brush painting, but is not limited to these methods.

A compound according to an exemplary embodiment of the present specification may be produced by a production method described later. Representative examples are described in the production examples described below, but as needed, substituents can be added or excluded, and the positions of the substituents can be changed. Additionally, starting materials, reactants, reaction conditions, etc. can be changed based on techniques known in the art.

In addition, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described in detail below. The embodiments of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

<Preparation example: Preparation of compounds 1 to 60>

Preparation Example 1. Preparation of compounds 1 to 10

(1) Preparation of Compound A

(4,8-bis(5-(2-ethylhexyl)-4-methoxythiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6 in a round flask equipped with a condenser. 10 g of -diyl)bis(trimethylstannane) was dissolved in 150 mL of toluene along with 0.43 g of Pd ₂ (dba) ₃ and 0.57 g of tri(o-tolyl)phosphine, and then refluxed. When the temperature reached 100°C, 5.15 g (2.5 eq) of ethyl 2-bromothiophene-3-carboxylate was dissolved in 5 mL of toluene, slowly injected, and refluxed for 12 hours. After the reaction was completed, the compound A (diethyl 2,2'-(4,8-bis(5-(2-ethylhexyl)-4-methoxythiophen-2-yl)benzo[1,2) was obtained through column chromatography. -b:4,5-b']dithiophene-2,6-diyl)bis(thiophene-3-carboxylate)) was obtained.

(2) Preparation of Compound B

Dissolve 8.16g (5.3eq) of 1-bromo-4-hexylbenzene in 200mL of THF in a round flask, then slowly inject 13.5mL of n-BuLi at -78°C for 1 hour. It was stirred at the same temperature. Compound A prepared in (1) was dissolved in 50 mL of THF, then slowly injected into a stirring round flask and stirred at room temperature for 12 hours. After extracting the organic layer with chloroform, the solvent was removed, dissolved in 100 mL of octane, 10 mL of acetic acid, and 1 mL of sulfuric acid, and refluxed at 65°C for 4 hours. The reaction was terminated with distilled water, and the compound B was obtained through column chromatography.

(3) Preparation of Compound C

In a round flask, 1 g of Compound B prepared in (2) above was dissolved in 100 mL of THF, and then 0.76 mL of n-BuLi was slowly injected at -78°C. After stirring at the same temperature for 1 hour, 0.5 mL of DMF was slowly added and stirred for 12 hours. After the reaction was terminated with distilled water, the organic layer was extracted and Compound C was obtained through column chromatography.

(4) Preparation of Compound 1

In a round flask equipped with a condenser, 1 g of compound C prepared in (3) above and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3- 0.7 g of oxo-2,3-dihydro-1H-inden-1-ylidene) malononitrile) was dissolved in 10 mL of chloroform, 1 mL of pyridine was added, and the mixture was refluxed at 60°C for 12 hours. Compound 1 was obtained through column chromatography after filtration through methanol.

(5) Preparation of compounds 2 to 10

In (4) above, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H-inden-1 The following compounds 2 to 10 were prepared by following the same process as (4), except that the materials in Table 1 below were used instead of -ylidene) malononitrile).

target compound materials used compound 2 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 3 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 4 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 5 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 6 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 7 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 8 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 9 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 10 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

[Compound 7]

[Compound 8]

[Compound 9]

[Compound 10]

Preparation Example 2. Preparation of compounds 11 to 20

(1) Preparation of compound B2

In (2) of Preparation Example 1, except that 1-bromo-3-hexylbenzene was used instead of 1-bromo-4-hexylbenzene. Then, the compound B2 was prepared in the same process as (2) of Preparation Example 1.

(2) Preparation of compound C2

Compound C2 was prepared through the same process as Preparation Example 1 (3), except that Compound B2 was used instead of Compound B in Preparation Example 1 (3).

(3) Preparation of compound 11

Compound 11 was prepared in the same manner as Preparation Example 1 (4), except that Compound C2 was used instead of Compound C in Preparation Example 1 (4).

(4) Preparation of compounds 12 to 20

In (3) of Preparation Example 2, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 12 to 20 were prepared by following the same process as (3) of Preparation Example 2, except that the materials in Table 2 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 12 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 13 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 14 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 15 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 16 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 17 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 18 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 19 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 20 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 12]

[Compound 13]

[Compound 14]

[Compound 15]

[Compound 16]

[Compound 17]

[Compound 18]

[Compound 19]

[Compound 20]

Preparation Example 3. Preparation of compounds 21 to 30

(1) Preparation of compound B3

(2) of Preparation Example 1, except that 2-hexylthiophene was used instead of 1-bromo-4-hexylbenzene in (2) of Preparation Example 1. ) Compound B3 was prepared in the same manner as above.

(2) Preparation of compound C3

Compound C3 was prepared in the same manner as Preparation Example 1 (3), except that Compound B3 was used instead of Compound B in Preparation Example 1 (3).

(3) Preparation of compound 21

Compound 21 was prepared in the same manner as Preparation Example 1 (4), except that Compound C3 was used instead of Compound C in Preparation Example 1 (4).

(4) Preparation of compounds 22 to 30

In (3) of Preparation Example 2, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 22 to 30 were prepared by following the same process as (3) of Preparation Example 2, except that the materials in Table 3 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 22 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 23 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 24 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 25 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 26 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 27 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 28 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 29 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 30 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 22]

[Compound 23]

[Compound 24]

[Compound 25]

[Compound 26]

[Compound 27]

[Compound 28]

[Compound 29]

[Compound 30]

Preparation Example 4. Preparation of compounds 31 to 40

(1) Preparation of Compound D

In (1) of Preparation Example 1, (4,8-bis(5-(2-ethylhexyl)-4-methoxythiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2 Instead of ,6-diyl)bis(trimethylstannane) (4,8-bis(5-((2-ethylhexyl)thio)-4-methoxythiophen-2-yl)benzo[1,2-b:4,5-b' ] Compound D was prepared in the same manner as (1) in Preparation Example 1, except that dithiophene-2,6-diyl)bis(trimethylstannane) was used.

(2) Preparation of Compound E

Compound E was prepared in the same manner as Preparation Example 1 (2), except that Compound D synthesized in Preparation Example 4 (1) was used instead of Compound A used in Preparation Example 1 (2). .

(3) Preparation of Compound F

Compound F was prepared in the same manner as Preparation Example 1 (3), except that Compound E synthesized in Preparation Example 4 (2) was used instead of Compound B used in Preparation Example 1 (3). .

(4) Preparation of compound 31

Compound 31 was prepared in the same manner as Preparation Example 1 (4), except that Compound F synthesized in Preparation Example 4 (3) was used instead of Compound C used in Preparation Example 1 (4). .

(5) Preparation of compounds 32 to 40

In (4) of Preparation Example 4, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H Compounds 32 to 40 below were prepared in the same manner as (4) in Preparation Example 4, except that the materials shown in Table 4 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 32 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 33 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 34 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 35 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 36 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 37 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 38 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 39 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 40 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 32]

[Compound 33]

[Compound 34]

[Compound 35]

[Compound 36]

[Compound 37]

[Compound 38]

[Compound 39]

[Compound 40]

Preparation Example 5. Preparation of compounds 41 to 50

(1) Preparation of compound E2

In (2) of Preparation Example 4, except that 1-bromo-3-hexylbenzene was used instead of 1-bromo-4-hexylbenzene. Then, the compound E2 was prepared in the same process as (2) in Preparation Example 4.

(2) Preparation of compound F2

Compound F2 was prepared in the same manner as (3) in Preparation Example 4, except that Compound E2 was used instead of Compound E in (3) of Preparation Example 4.

(3) Preparation of compound 41

Compound 41 was prepared in the same manner as Preparation Example 4 (4), except that Compound F2 was used instead of Compound F in Preparation Example 4 (4).

(4) Preparation of compounds 42 to 50

In (3) of Preparation Example 5, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H Compounds 42 to 50 below were prepared in the same process as (3) of Preparation Example 5, except that the materials shown in Table 5 below were used instead of -inden-1-ylidene)malononitrile).

target compound materials used Compound 42 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 43 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 44 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 45 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 46 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 47 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 48 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 49 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 50 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 42]

[Compound 43]

[Compound 44]

[Compound 45]

[Compound 46]

[Compound 47]

[Compound 48]

[Compound 49]

[Compound 50]

Preparation Example 6. Preparation of compounds 51 to 60

(1) Preparation of compound E3

(2) of Preparation Example 4, except that 2-hexylthiophene was used instead of 1-bromo-4-hexylbenzene in (2) of Preparation Example 4. ) Compound E3 was prepared in the same manner as above.

(2) Preparation of compound F3

Compound F3 was prepared in the same manner as (3) in Preparation Example 4, except that Compound E3 was used instead of Compound E in (3) of Preparation Example 4.

(3) Preparation of compound 51

Compound 51 was prepared in the same manner as Preparation Example 4 (4), except that Compound F3 was used instead of Compound F in Preparation Example 4 (4).

(4) Preparation of compounds 52 to 60

In (3) of Preparation Example 6, 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2-(3-oxo-2,3-dihydro-1H The following compounds 52 to 60 were prepared by following the same process as (3) of Preparation Example 6, except that the materials in Table 6 below were used instead of -inden-1-ylidene)malononitrile).

The UV-Vis spectra of the prepared compounds 1 to 60 in the film state are shown in Figures 2 to 61.

target compound materials used Compound 52 2-(6-fluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-fluoro-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 53 (2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile) Compound 54 2-(6-methyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-methyl-3-oxo-2,3-dihydro-1H-inden-1- ylidene) A compound mixed with malononitrile in a mass ratio of 3:7 Compound 55 2-(5,6-dimethyl-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile Compound 56 2-(6-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(5-bromo-3-oxo-2,3-dihydro-1H-inden-1- A compound in which ylidene)malononitrile is mixed at a mass ratio of 3:7 Compound 57 2-(6-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene) A compound containing malononitrile and 2-(5-chloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile mixed at a mass ratio of 3:7 Compound 58 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile Compound 59 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile Compound 60 2-(6-oxo-5,6-dihydro-4H-cyclopenta[b]thiophen-4-ylidene)malononitrile

[Compound 52]

[Compound 53]

[Compound 54]

[Compound 55]

[Compound 56]

[Compound 57]

[Compound 58]

[Compound 59]

[Compound 60]

<Example: Manufacturing of organic solar cell>

Example 1.

(1) Preparation of composite solution

The following compound poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene) )-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5 '-c']dithiophen-4,8-dione))](poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1, 2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'- bis(2-ethylhexyl)benzo[1 ',2'-c:4',5'-c']dithiophene-4,8-dione))], PBDB-T) (Mn: 25,000 g/mol, Solarmer) as an electron donor material, prepared above Compound 1 synthesized in the example was used as an electron acceptor and was dissolved in chlorobenzene (CB) at a mass ratio of 1:1 to prepare a composite solution with a concentration of 2 wt%.

(2) Manufacturing of organic solar cells

A glass substrate (11.5Ω/□) coated with ITO in a 1.5×1.5cm ² bar type was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was treated with ozone for 10 minutes. 1 Electrode was formed.

After spin-coating a ZnO nanoparticle solution (N-10, Nanograde Ltd, 2.5wt% in 1-butanol, filtered through 0.45㎛ PTFE) on the first electrode at 4,000rpm for 40 seconds, An electron transport layer was formed by heat treatment at 80°C for 10 minutes to remove the remaining solvent.

Thereafter, the composite solution prepared in (1) was spin-coated on the electron transport layer at 70°C at 900 rpm for 25 seconds to form a photoactive layer, and MoO ₃ was applied on the photoactive layer at a speed of 0.2 Å/s and 10 A hole transport layer was formed by thermal evaporation to a thickness of 10 nm under ^-7 torr vacuum.

Afterwards, Ag was deposited to a thickness of 100 nm at a speed of 1 Å/s inside a thermal evaporator to form a second electrode, thereby manufacturing an organic solar cell with an inverted structure.

Examples 2 to 60.

Organic solar cells of Examples 2 to 60 were prepared in the same process as Example 1, except that Compounds 2 to 60 were used instead of Compound 1 when preparing the composite solution in Example 1.

Comparative Example 1.

An organic solar cell was prepared in the same manner as in Example 1, except that Comparative Compound 1 below was used instead of Compound 1 when preparing the composite solution in Example 1.

[Comparative compound]

The photoelectric conversion characteristics of the organic solar cells prepared in Examples 1 to 60 and Comparative Example 1 were measured under 100 mW/cm ² (AM 1.5) conditions, and the results are shown in Table 7 below.

Spin-speed (rpm) V _oc
(V) J _sc
(mA/ ^cm2 ) FF η
(%) Example 1 900 0.916 16.628 0.566 8.63 Example 2 900 0.901 15.766 0.618 8.78 Example 3 900 0.750 15.343 0.735 8.47 Example 4 900 0.757 15.093 0.727 8.31 Example 5 900 0.744 16.676 0.683 8.48 Example 6 900 0.737 16.292 0.683 8.20 Example 7 900 0.740 14.947 0.682 7.55 Example 8 900 0.733 14.680 0.688 7.41 Example 9 900 0.919 16.397 0.484 7.30 Example 10 900 0.914 16.311 0.459 6.84 Example 11 900 0.924 17.151 0.523 8.28 Example 12 900 0.920 16.204 0.475 7.09 Example 13 900 0.901 16.817 0.485 7.34 Example 14 900 0.901 16.662 0.524 7.87 Example 15 900 0.922 16.770 0.526 8.14 Example 16 900 0.919 16.397 0.484 7.30 Example 17 900 0.901 17.295 0.544 8.47 Example 18 900 0.832 14.507 0.651 7.85 Example 19 900 0.828 15.610 0.678 8.77 Example 20 900 0.833 15.592 0.649 8.44 Example 21 900 0.820 15.628 0.665 8.52 Example 22 900 0.898 12.106 0.664 7.21 Example 23 900 0.897 12.694 0.657 7.49 Example 24 900 0.908 14.013 0.662 8.42 Example 25 900 0.903 13.899 0.677 8.49 Example 26 900 0.879 14.771 0.649 8.43 Example 27 900 0.876 15.198 0.654 8.72 Example 28 900 0.918 17.855 0.530 8.68 Example 29 900 0.926 17.424 0.525 8.46 Example 30 900 0.927 17.878 0.521 8.64 Example 31 900 0.928 17.913 0.551 9.16 Example 32 900 0.919 18.046 0.595 9.87 Example 33 900 0.916 17.858 0.574 9.39 Example 34 900 0.916 17.865 0.575 9.41 Example 35 900 0.878 18.432 0.546 8.83 Example 36 900 0.918 17.936 0.607 9.99 Example 37 900 0.914 18.431 0.616 10.38 Example 38 900 0.840 17.960 0.683 10.30 Example 39 900 0.839 17.861 0.684 10.24 Example 40 900 0.841 17.468 0.690 10.14 Example 41 900 0.838 17.761 0.687 10.22 Example 42 900 0.904 17.624 0.558 8.90 Example 43 900 0.921 18.312 0.543 9.16 Example 44 900 0.925 15.547 0.656 9.44 Example 45 900 0.923 14.961 0.663 9.16 Example 46 900 0.755 16.055 0.727 8.82 Example 47 900 0.925 17.168 0.629 9.98 Example 48 900 0.924 17.202 0.639 10.16 Example 49 900 0.926 16.502 0.650 9.94 Example 50 900 0.924 16.372 0.652 9.86 Example 51 900 0.910 16.053 0.644 9.40 Example 52 900 0.919 17.032 0.580 9.07 Example 53 900 0.916 16.628 0.566 8.63 Example 54 900 0.926 16.502 0.650 9.94 Example 55 900 0.924 16.372 0.652 9.86 Example 56 900 0.925 17.168 0.629 9.98 Example 57 900 0.924 17.202 0.639 10.16 Example 58 900 0.910 16.053 0.644 9.40 Example 59 900 0.901 15.766 0.618 8.78 Example 60 900 0.919 17.032 0.580 9.07 Comparative Example 1 900 0.739 17.869 0.523 6.91

In Table 7, Spin-speed is the rotation speed of the equipment when forming a photoactive layer by spin-coating the composite solution on the electron transport layer, V _OC is the open-circuit voltage, J _SC is the short-circuit current, and FF is the charging rate. (Fill factor) and η means energy conversion efficiency. The open-circuit voltage and short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell. Additionally, the fill factor is the area of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. Energy conversion efficiency (η) can be obtained by dividing the product of the open-circuit voltage (V _oc ), short-circuit current (J _sc ), and charging rate (FF) by the intensity of incident light (P _in ), and the higher this value, the more preferable. .

Looking at the results in Table 7, the organic solar cells of Examples 1 to 60 using Compounds 1 to 60 according to an embodiment of the present specification as electron acceptors are similar to the organic solar cells of Comparative Example 1 using a comparative compound not containing an alkoxy group. It can be seen that compared to batteries, the open-circuit voltage is high, the device efficiency such as charging rate is excellent, and the energy conversion efficiency is excellent.

In addition, it can be confirmed that the energy conversion efficiency of Examples 31 to 60 using Compounds 31 to 60 containing both an alkoxy group and an alkylthio group is superior to that of Examples 1 to 30 using Compounds 1 to 30 containing an alkoxy group and an alkyl group. .

100: first electrode
200: Photoactive layer
300: second electrode

Claims (11)

Heterocyclic compounds represented by any one of the following formulas 3-1 to 3-4:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

In Formulas 3-1 to 3-4,
R1 to R4 are each hydrogen; or an alkyl group having 1 to 10 carbon atoms,
R5 to R8 are each hydrogen,
R10 and R13 are each an alkoxy group having 1 to 10 carbon atoms,
R9, R11, R12 and R14 are each hydrogen; an alkyl group having 1 to 20 carbon atoms; or an alkylthio group having 1 to 20 carbon atoms,
R15 to R22 are each hydrogen,
L1 to L4 are each a phenylene group; or a divalent thiophene group,
Y1 and Y2 are each hydrogen; halogen group; or an alkyl group having 1 to 10 carbon atoms,
n and m are each integers from 0 to 6. delete delete In claim 1,
The above formula 3-1 is represented by the following formula 4-1 or 4-5,
The above formula 3-2 is represented by the following formula 4-2 or 4-6,
The above formula 3-3 is represented by the following formula 4-3 or 4-7,
The above formula 3-4 is a heterocyclic compound represented by the following formula 4-4 or 4-8:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

In Formulas 4-1 to 4-8,
R1 to R14, Y1, Y2, n and m are the same as defined in Formulas 3-1 to 3-4 above,
R15 to R22 are each hydrogen,
Q1 to Q4 are each S. In claim 1,
R9 and R12 are each an alkyl group having 1 to 20 carbon atoms; or an alkylthio group having 1 to 20 carbon atoms,
R10 and R13 are each an alkoxy group having 1 to 10 carbon atoms,
A heterocyclic compound wherein R11 and R14 are each hydrogen. In claim 1,
A heterocyclic compound wherein R9 and R12 are each an alkylthio group having 1 to 20 carbon atoms. In claim 1,
The above formula 3-1 has the following formulas 5-1 to 5-7, 5-11 to 5-17, 5-21 to 5-27, 5-31 to 5-37, 5-41 to 5-47 and 5- Any one selected from 51 to 5-57,
The formula 3-2 is any one selected from the following formulas 5-8, 5-18, 5-28, 5-38, 5-48, and 5-58,
The formula 3-3 is any one selected from the following formulas 5-10, 5-20, 5-30, 5-40, 5-50, and 5-60,
The formula 3-4 is a heterocyclic compound selected from the following formulas 5-9, 5-19, 5-29, 5-39, 5-49, and 5-59:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

[Formula 5-12]

[Formula 5-13]

[Formula 5-14]

[Formula 5-15]

[Formula 5-16]

[Formula 5-17]

[Formula 5-18]

[Formula 5-19]

[Formula 5-20]

[Formula 5-21]

[Formula 5-22]

[Formula 5-23]

[Formula 5-24]

[Formula 5-25]

[Formula 5-26]

[Formula 5-27]

[Formula 5-28]

[Formula 5-29]

[Formula 5-30]

[Formula 5-31]

[Formula 5-32]

[Formula 5-33]

[Formula 5-34]

[Formula 5-35]

[Formula 5-36]

[Formula 5-37]

[Formula 5-38]

[Formula 5-39]

[Formula 5-40]

[Formula 5-41]

[Formula 5-42]

[Formula 5-43]

[Formula 5-44]

[Formula 5-45]

[Formula 5-46]

[Formula 5-47]

[Formula 5-48]

[Formula 5-49]

[Formula 5-50]

[Formula 5-51]

[Formula 5-52]

[Formula 5-53]

[Formula 5-54]

[Formula 5-55]

[Formula 5-56]

[Formula 5-57]

[Formula 5-58]

[Formula 5-59]

[Formula 5-60]
first electrode;
a second electrode provided opposite the first electrode; and
It is provided between the first electrode and the second electrode, and includes one or more organic layers including an organic active layer,
An organic electronic device wherein the organic active layer includes the heterocyclic compound according to any one of claims 1 and 4 to 7. In claim 8,
The organic active layer includes an electron donor and an electron acceptor,
An organic electronic device wherein the electron acceptor includes the heterocyclic compound. In claim 8,
The organic electronic device is an organic solar cell, an organic photoelectric device, an organic light-emitting device, an organic photoreceptor, or an organic transistor. forming a first electrode on a substrate;
forming one or more organic layers including an organic active layer on the first electrode; and
Comprising the step of forming a second electrode on the organic layer,
A method of manufacturing an organic electronic device wherein the organic active layer includes the heterocyclic compound according to any one of claims 1 and 4 to 7.